Anthraquinone dyes for animal and related fibers



taupe to brown shad Patented Nov. 21 1944 i oFFICE assaoeefl ANT HRAQ UINONE DYESFORANIMALAND ltELATEDFIBERS y Henry R. Lee, Pitman, N. J., and Charles 1 A.

Young, .Wilmington, Del., assignors to E; I. du

Pont de Nemours & Company, Wilmingto n.

. Del.,-a corporation of Delaware g. Application May 23,1942, SerialNo. 444,274

6 Claims, 1 (01. 260-3 3) paration of No Drawin This invention relates tothe pre new-dyesfor animal and relatedfibers and more particularly the preparationbf new anthrfaq u none wool "dyes which dye in desirable gray and these are of a ,li

mited range in shade, dyeing wool and related stirred at tempera fibers in bluish gray. to lavender prefarablyat 20, to 40 tures o from sulfonic acid class whichmay be used with known 4 colors of that class having similar application characteristics whereby the" usefulness of that class of fast' colors may'be enlarged ing of animal and rela'ted fib in the dyeeslhaving outstanding fast, 5 ers. J 1 i l i ness properties. i I p y We have found that where 1,1-dianthrimides it While in the field of dyesfor wool, silk and which carry at least 1 free amino group in the related 'fibers a, wide rangeof colors have been alpha position para to the imino-linkage are sub developed and are available for use today to pro- 4 jectedto acylation, preferably with an a lipha tic duce a wide variety of shades there is still an acylating agent, then sulfonated toimake'the effort beingmade to produce colors in this class productwater solublje and theresulting acylami with improved dyeing andfastness properties as nodianthrimide sulfonic acid derivative then sub- .well -as a wider variety' ofshades. Easeof applijected to the action of areducing agentin sul cation to give the shade desiredpcompatibility of furic acid, new and valuable acid wool dyes are colors in mixtures,'the levelness with which the producedjwhich dye in desirable gray and taupe dye is absorbed by the fiber, its fastness with reto brown shades of good application and excel spect to the multifolduconditions to which the lent fastness properties; particular fabric must subjected, the afiinity f The newdyes'may be produced from l-amino ofqa particularcolor for the fiber, especially im- 1 1,1" dian hrimi "-d a n iy d t f portanttwhen the color must be usedin mixtures, mide and 4-amino-4f-hydroxy1,1'-dianthrimide areall qualities that mustbe'taken intoyconsiderand their halogenation and simple substitution ation in developing new colors for the market derivatives, by acylating the 4-amino-1,1'-diantoday. @Itgisfrecognizedythat many of the comthrimide compound in concentrated sulfuric acid mercial dyes are lamentablydeficientin someof o f from 98% to 35% "oleu n, andat temperatures their; dyeing or fastness;properties; but until off from 20 to 100 C.,then adding sufiicient oleum more desirable colors can be producedvthese tobring the solution to f ror'n l 5%to 35%,oleum deficientcolors-must still be employed if a shade to efiect sulfonati n of the p ct a emp r: requiring such a color 'isin demand. f atures of from 40 C, to 1,009 C. .When sulfona In searching for fastercolorsinthe 'anthraquia tion is completethe mass iscooied andthe acid nonewool color class certain'simpl'e substitutedconcentration is brought to from 85%,toQ lQ0% LU-dianthrimidesulfonic acids have been pro- "with water or dilute acid, a small amount of duced whichshow good fastness properties, but reducing agent is then addedand the mass is gray shades. Since dyeswof equal fastness propin the co l or of the solution occurs] li'he water ertiesand similar'dyeing characteristics with: soluble dy sthus produced may be-i datjedb which to shade these-ycolors: are not available, any of the methodsusually employedin isolat these colorsare limitedgintheir usefulness. Furing water soluble anthraquinone sulfonie acids. thermore it is desirable in any class to have a such as by drowning the mass in anaqueous soluf i variety, Of shades so that relatively little mixing, tion of sodium chloride, filtering, washing the enceptfor shading purposes is requirede Inview cake with salt solution and drying. Where the or therwideruse ofineutral gray, taupe and brown acylation is carried out in oleum at the higher shades in upholstering material; rugs; etc, there temperatures, sulfonation may be effected simulreat demand for colors for wool in this taneously therewith, In acylating the "amino- .colonrangeWhich havegood application andexdianthrimide the acid halides, gacid anhydrides ceptional fastness properties, particularly to or'the'anhydrous acids maybe employed.

light i i r i I The following examplesare given to illustrate i It i ef r an biect of this. invention to ytheyinve ntion; The parts used are by weightpffl provide .n w dyes for W001. and related fibers, i i i w i i i i i in the anthraquinone seIiES,1WhiCh dye in neutral Emmpzeel 1. Y i gray and taupe to brown shades, which have To a solution of 25 parts of 4,4"-diamin-o-1,1'- good application and exceptional fastness prop dianthrimide in 150 partsof 100% sulfuric "acid erties,particularlytolight. It isa further obisadded slowly at 25-30 C. 10 parts of acetyl ject of the: invention :to provide new colors for chloride The jresulting solution is stirred at ,wool; silkand nylonvin the 1,1'-dianthrimide 50'55 C. for two-hours.

wool brownish violet shades.

' water.

20-50 C. One part of copper powder is then added, and the mixture stirred at 20-30 C. for

-15 hours, until the color of the sulfuric acid solution has changed from green to brown, and

v the product forms a brown solution in water. The

product is isolated by pouring the reaction mass into a cooled sodium chloride solution, filtering off the precipitated color, washing with more salt solution and finally drying. The new product dyes wool in strong taupe shades having excellent fastness properties.

In place of acetyl chloride employed in this preparation there may be used equivalent amounts of acetic anhydride or glacial acetic acid; 1

Instead of copper powder there may be employed ferrous sulfate or iron, aluminum or zinc powder as the reducing agent.

Examlple 2 6.5 parts of acetic anhydride. is added slowly at -30 C. to a solution of 25 parts of 4,4'-diamino- 1,1'-dianthrimide in 300 parts of 31% oleum. The resultingmixture is stirred at 45-55 C. for two hours, at the end of which time the product is completely soluble in hot water. Then the mass is stirred at 90-95 C. for one-half hour, after which it is cooled and parts of water is added at 2'0-50 C. After cooling to 30 C., 1.5 parts of copper powder is added, and the mass stirred at 20-30" C. for -15 hours. The reaction mass is drowned in 'sodium chloride solution, and the crude color is filtered off, washed and dried. The product is similar to that obtained in Example 1.

Example 3 To a solutionof 15 parts of 4-amino-1,l-dianthrimide in 90 parts of 100% sulfuric acid is added 6 parts of acetyl chloride, and the mass is stirred at 50-55 C. for two hours. 90 parts of 63-65% oleum is then added, andthe resulting solution stirred at 90-100 C. for one-half hour. The mass is cooled and 13 parts of water added. The product at this point forms a brown solution with concentrated sulfuric acid and dyes T the cooled and diluted sulfonation mass is added 0.9 part of copper powder and the mixture stirred for fifteen hours. The product, which is isolated as described in-Example 1, imparts an olive color to concentrated sulfuric acid and dyes wool attractive brown shades. If aluminum powder is added to the diluted sulfonation mass instead of copper powder, a product is obtained which dyes wool somewhat greener shades.

Example 4 thrimide is dissolved in 150 parts of 100% sulfuric acid. To this solution is added 10 parts of acetyl chloride and the mixture stirred at -55 C. for two hours. Then 150 parts of 65% oleum is added and mass stirred at 90-95 C. for one-half hour, or until the product is completely soluble in Warm The sulfonated product dyes wool in grayish blue shades from a reddish blue solution. To the sulfonation mass is added 22 parts of water, and after cooling to 30? C. 1.5 parts of copper powder is added. The mixture is stirred at 20-30 C. for twelve hours and the product isolated by drowning in water, followed by the addition of sodium chloride, filtering, washing and drying. The product forms a green solution with concentrated sulfuric acid, a lavender solution.

with watenand dyes wool neutral gray shades. The use of aluminum in place of copper powder results in the formation of a product which dyes wool somewhat greener shades.

Example 5 11.8 parts of propionyl chloride is added to a solution of 25 parts of 4,4'-diamino-1,l-dianthrimide in 150 parts of 100% sulfuric acid. The mixture is stirred at -55 C. for two hours. 150 parts of oleum is then added, and the mass is stirred at -95 C. for one-half hour.

At the end of this time the mass is cooled and 22 parts of water added. The product at this point I forms a lavender solution in'water-and dyes wool lavender-gray shades. After coolingthe reaction mass to 30 C., 1.5 parts of copper powder is added, and the mixture stirred at 20 -30 C. for sixteen hours. The product, which is isolated from the reaction mass according to the method described in Example 1, formsa brown solution with water and dyes wool in attractive taupe shades. l I

Example 6 To a solution of 25 parts of 4,4'-diamino-1,1'- dianthrimide in 150 parts of sulfuric acidis added 17.9 parts of benzoyl chloride and the mixture is stirred at 50-55 C. for two hours. Then parts of 63.5% oleum is added and the mass stirred at 9095 C. for one-half hour, after which the charge is cooled and 22 parts of water added. The product at this point forms a green solution with concentrated sulfuric acid, a violet solution with water, and dyes wool in reddish gray shades. On addition of 1.5 parts of copper powder and stirring at 20-30 C. for sixteen hours, the color of the sulfuric acid solution becomes brown, the product forms an olive-gray solution with water and'dyes wool in olive-gray shades. The new color is isolated as described in Example 1.

In the above examples'the aminodianthrimid mide, after isolation, may be sulfonated in oleum V and subjected to the action of the reducing agent in sulfuric acid as described in the examples. Acylation in sulfuric acid, however, is preferred for by this process isolation of the acyldianthrimide is made urmecessary.

It is of course understood that other acylating agents than those mentioned in the specific examples are contemplated as coming within the scope of the present invention, those given in the specific examples being used merely to exemplify the invention. The higher homologues and substitution derivatives of both the aliphatic and aromatic acylating agents may be employed such as for example isobutyric anhydride, caproyl chloride, ortho-chloro-benzoyl chloride, paraanisic anhydride, cuminic anhydride, and metacarboxy-benzene sulfonyl chloride. The amountof sulfuric acid or oleum employed should be sufficient to completely dissolve the starting material and the final oleum concentration should be such that sulfonation will be effected at temperatures preferably below 150 Cl In effecting conversion of the sulfonated acylaminodianthrimides to the new colors of this invention reducing agents such as metals and metal salts which havea reducing actionin concentrated sulfuric acid may be employed, such ascfor example copper, aluminum, zinc, iron and reducing salts of such metals as for example, ferrous questionably takes place during the sulfonation product'is'f'not completely acylated. Some deacylation also unreaction particularly at'the higher temperatures.

During the treatmentof the acylaminodianthri mide with the reducing agent in sulfuric acid where the reaction is'carried out without isolation of the product or removal of the excess ,acylating agent present itis possible that some af'cylation takesplace, but even then the final product is not completely acylated. It has also been/impossible to determine the exact molecular struc-- ture of theproduct resulting from the reaction of the reducing agent in sulfuric acid on the acylated-aminodianthrimide and while it is believed lent fastness properties.

in the 4'-position a substituentof the group consisting of H, OH and NH-z, sulfonating the resulting product in oleum and subjecting the resulting acylated amino-1,1'-dianthrimide sulfonic acid to the action of a reducing agent in sulfuric, acid at temperatures of from 0 to 100 01., which dyestuffs dye wool and related fibers in gray and taupe to brown shades exhibiting excellent fastness properties. i

3. The dyestufis which are obtained by acylat ing 4,4 diamino-LF-dianthrimide, sulfonating the resulting product and subjecting the acylated 4,4-diamino-1,1'-dianthrimide sulfonic acid to,

the action of a reducing agent in sulfuric acid, which products dye wool and related fibers in gray and taupe to brown shades exhibiting excel- 4. The dyestuffs which are obtained by subjecting 4,4'-diamino-l,1'-dianthrimide to acylation: g with an aliphatic acylating agent, sulfonatingfth resulting product and subjecting the acylated diaminodianthrimide sulfonic acid to the action of a reducing agent in sulfuric acid, which dyestuffs dye wool and'related fibers in taupe shades of excellent fastness properties.

5. The dyestufi which is obtained by subjecting 4,4'-diamino-1,1'-dianthrimide to acetylation and that a ring closure of som type is effected, bee

cause of the radical change in the dyeing properties of the resulting products, it is impossible to} definitely state the, nature condensation.

We claim: 1. The dyestuffs which are obtained by agylating a 4-amino-1,1-dianthrimide, sulfonatingthe of this ring closure or resulting product in oleum and subjecting thev resulting acylated amino-1,1-dianthrlmide.zsulfonic acid to the action of a reducing agent in sulfuric acid at temperatures of from 0 0 100,

0;, which dyestuffs dye Wool and related fibers in gray and taupe to brown shades exhibiting excellent fastness properties. 2. The dyestuffs which are obtainedby acylat- ,sulfonation and subjecting the resulting acetyl ated diamino dianthrimide sulfonic acid to the reaction of a reducing agent in sulfuric acid,

which dyestuff dyes wool V taupe shades of excellent fastnessproperties.

6. The dyestuff which is obtained by subjecting 4-amino-4-hydroxy-1,1'-dianthrimide to acetylation and sulfonation and subjectingthe resulting acetyl-amino-hydroxy-dianthrimide sulfonic acid to the action of a reducing agent in sulfuric acid,

which dyestuffs dye wool and related fibers in 1 neutralgray shades of excellentfastness properties. l

i HENRY R. LEE.

CHARLES A. YOUNG.

ing a 4-amino-1,1'-dianthrimide, which. carries and related fibers in 

